WO2012132091A1 - Redox-flow battery and method of operating thereof - Google Patents
Redox-flow battery and method of operating thereof Download PDFInfo
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- WO2012132091A1 WO2012132091A1 PCT/JP2011/075933 JP2011075933W WO2012132091A1 WO 2012132091 A1 WO2012132091 A1 WO 2012132091A1 JP 2011075933 W JP2011075933 W JP 2011075933W WO 2012132091 A1 WO2012132091 A1 WO 2012132091A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04753—Pressure; Flow of fuel cell reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04761—Pressure; Flow of fuel cell exhausts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04791—Concentration; Density
- H01M8/04798—Concentration; Density of fuel cell reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04791—Concentration; Density
- H01M8/04805—Concentration; Density of fuel cell exhausts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a redox flow battery and an operation method thereof.
- the present invention relates to a redox flow battery capable of obtaining a high electromotive force.
- a redox flow battery as one of large-capacity storage batteries.
- charge and discharge are performed by supplying a positive electrode electrolyte and a negative electrode electrolyte respectively to a battery element in which a diaphragm is interposed between a positive electrode and a negative electrode.
- the electrolytic solution typically, an aqueous solution containing metal ions whose valence changes by oxidation-reduction is used.
- Typical examples include an iron-chromium redox flow battery using iron ions for the positive electrode and Cr ions for the negative electrode, and a vanadium redox flow battery using V ions for both the positive electrode and the negative electrode (for example, JP-A-2006-147374). Publication (Patent Document 1)).
- Vanadium-based redox flow batteries have been put into practical use and are expected to be used in the future.
- the conventional iron-chromium redox flow battery and vanadium redox flow battery cannot be said to have a sufficiently high electromotive force.
- a new redox that has a higher electromotive force and can stably supply metal ions used in active materials, preferably stably and inexpensively. Development of a flow battery is desired.
- one of the objects of the present invention is to provide a redox flow battery capable of obtaining a high electromotive force.
- Another object of the present invention is to provide a redox flow battery operating method capable of maintaining a state having excellent battery characteristics.
- the standard redox potential of the metal ion of the positive electrode active material used in the conventional redox flow battery is 0.77V for Fe 2+ / Fe 3+ and 1.0V for V 4+ / V 5+ .
- the present inventors are water-soluble metal ions as the metal ions of the positive electrode active material, have a higher standard redox potential than conventional metal ions, are relatively cheaper than vanadium, and are excellent in terms of resource supply.
- the redox flow battery using manganese which is considered to be
- the standard oxidation-reduction potential of Mn 2+ / Mn 3+ is 1.51 V, and Mn ions have preferable characteristics for constituting a redox pair having a larger electromotive force.
- the redox flow battery is a battery using an aqueous solution as an electrolyte. Therefore, in this redox flow battery, hydrogen gas may be generated at the negative electrode and oxygen gas may be generated at the positive electrode due to water decomposition as a side reaction accompanying the charge / discharge reaction.
- the oxidation-reduction potential of Mn as the positive electrode active material has been conventionally used as the positive electrode active material. It has been found that the side reaction at the positive electrode is dominant because it has a more noble potential than Fe and V.
- the state of charge of the negative electrode electrolyte (SOC: State of Charge, sometimes referred to as charge depth) gradually becomes higher than that of the positive electrode electrolyte.
- SOC State of Charge
- charge depth the state of charge of the negative electrode electrolyte
- the redox flow battery of the present invention is stored in a positive electrode electrolyte stored in a positive electrode tank and in a negative electrode tank in a battery element including a positive electrode, a negative electrode, and a diaphragm interposed between the two electrodes. It is a redox flow battery that charges and discharges by supplying a negative electrode electrolyte.
- the positive electrode electrolyte in the redox flow battery of the present invention contains Mn ions as the positive electrode active material, and the negative electrode electrolyte contains at least one of Ti ions, V ions, and Cr ions as the negative electrode active material.
- the redox flow battery of the present invention communicates from the outside to the inside of the negative electrode tank, and the negative electrode side introduction pipe for introducing the oxidizing gas into the negative electrode tank, and the negative electrode tank through the negative electrode side introduction pipe And a negative electrode side supply mechanism for supplying an oxidizing gas therein.
- the operation method of the redox flow battery of the present invention is an operation method of the redox flow battery using the above redox flow battery of the present invention, in order to oxidize the negative electrode active material contained in the negative electrode electrolyte, The oxidizing gas is introduced into the inside.
- the redox flow battery of the present invention when the charge state between the positive electrode electrolyte and the negative electrode electrolyte is different while charging and discharging are repeated, an oxidizing gas is introduced into the negative electrode electrolyte.
- the difference can be reduced by oxidizing the negative electrode electrolyte. If the difference between the charged states of both electrolytes is reduced, the battery capacity of the redox flow battery can be restored to a state close to the initial battery capacity.
- the oxidizing gas is preferably a gas containing oxygen.
- the oxidizing gas is not particularly limited as long as the negative electrode electrolyte can be oxidized, and may be, for example, chlorine. However, in consideration of safety when handling the oxidizing gas, it is preferable to use a gas containing oxygen, for example, pure oxygen, ozone, or air.
- the above-described redox flow battery of the present invention preferably includes a gas phase communication pipe that communicates the gas phase of the positive electrode tank and the gas phase of the negative electrode tank.
- oxygen gas is generated as a side reaction on the positive electrode side. Therefore, if the gas-phase communication pipe is provided, the oxygen gas generated on the positive electrode side can be used for oxidation of the negative electrode electrolyte. By always opening the gas phase communication pipe, oxygen gas can be introduced from the positive electrode tank to the negative electrode tank.
- the gas phase communication pipe may be normally closed and may be opened when the oxidizing gas is introduced from the negative electrode side introduction pipe into the negative electrode tank.
- the above-described redox flow battery of the present invention preferably includes a monitor mechanism for monitoring the state of charge of the redox flow battery.
- Examples of the monitoring mechanism include using a monitor cell having the same configuration as the battery element.
- the monitor cell may be configured to supply positive and negative electrolytic solutions actually used from the positive electrode tank and the negative electrode tank.
- a monitor mechanism for example, a transparent window provided in a pipe connecting the tank and the tank and the battery element
- Ti ions are used as the negative electrode active material
- the solution of trivalent Ti ions (Ti 3+ ) is black
- the solution of tetravalent Ti ions (Ti 4+ ) is almost transparent.
- the state of charge of both electrolytes can be determined to be comparable.
- the negative electrode side introduction pipe provided in the redox flow battery of the present invention is opened in the liquid phase of the negative electrode tank.
- the negative electrode side introduction pipe may be opened in the gas phase, but opening in the liquid phase can oxidize the negative electrode electrolyte more efficiently.
- the above-described redox flow battery of the present invention preferably includes a stirring mechanism provided inside the negative electrode tank and stirring the negative electrode electrolyte.
- the negative electrode electrolyte can be efficiently oxidized by stirring the negative electrode electrolyte.
- the effect is improved by combining with opening the negative electrode side introduction pipe into the liquid phase.
- the positive electrode electrolyte used in the above redox flow battery of the present invention preferably contains Ti ions.
- the negative electrode electrolyte when the positive electrode electrolyte contains Mn ions and Ti ions, the negative electrode electrolyte preferably contains Ti ions as the negative electrode active material, and further contains Mn ions.
- the above configuration is a configuration in which the metal ion species in the positive electrode electrolyte and the metal ion species in the negative electrode electrolyte are equal.
- the metal ions move to the counter electrode through the diaphragm of the battery element, effectively avoiding the phenomenon of battery capacity reduction due to the relative reduction of the metal ions that originally react at each electrode Yes
- (2) Liquid transfer with charge / discharge over time (a phenomenon in which the electrolyte solution of one electrode moves to the other electrode through the diaphragm) causes variations in the electrolyte volume and ion concentration of both electrodes Even if this occurs, effects such as (3) excellent electrolyte solution manufacturability can be obtained by mixing the electrolyte solutions of both electrodes and the like.
- the redox flow battery of the present invention preferably includes a liquid phase communication pipe that communicates the liquid phase of the positive electrode tank and the liquid phase of the negative electrode tank.
- both electrolytes may be mixed.
- the redox flow battery is completely discharged.
- a Ti / Mn electrolyte it is preferable to oxidize the mixed electrolyte after mixing both electrolytes and complete discharge state. Can be easily identified. This is because the Ti / Mn electrolyte solution becomes transparent when discharged.
- the redox flow battery of the present invention communicates from the outside of the positive electrode tank to the inside, and introduces a positive electrode side introduction pipe for introducing an oxidizing gas into the positive electrode tank, and a positive electrode side introduction It is preferable to include a positive electrode side supply mechanism that supplies the oxidizing gas into the positive electrode side tank through a pipe.
- the mixed electrolyte can be rapidly oxidized when both the electrolytes are mixed by opening the liquid phase communication pipe.
- the introduction of the oxidizing gas is preferably performed when the charge states of the positive electrode electrolyte and the negative electrode electrolyte are different.
- ⁇ Efficient redox flow battery operation can be performed by correcting the difference between the charged states of the two electrolytes. Unlike this configuration, the redox flow battery can be operated while introducing the oxidizing gas into the negative electrode tank.
- the charged state of the positive electrode electrolyte and the negative electrode electrolyte are made substantially the same by controlling the amount of oxidizing gas introduced.
- the amount of oxidizing gas introduced may be adjusted based on the monitoring results of monitoring the state of charge of both electrolytes using a monitor cell. In this way, by aligning the state of charge of both electrolytes, it is possible to lengthen the time until a difference occurs between the states of charge of both electrolytes.
- the transparency of the negative electrode electrolyte may be used.
- the operation method of the redox flow battery of the present invention it is preferable to operate while monitoring the charge state of the redox flow battery.
- the transparency of the electrolyte solution may be used, and if it is a redox flow battery equipped with a monitor cell, the monitor cell may be used.
- the redox flow battery of the present invention is a redox flow battery having a high electromotive force and capable of recovering a decrease in battery capacity caused by charging and discharging. Moreover, the operating method of the redox flow battery of the present invention can recover the reduced battery capacity when the battery capacity of the redox flow battery of the present invention decreases due to charging / discharging.
- FIG. 1 is a schematic diagram of a redox flow battery shown in Embodiment 1.
- FIG. It is a schematic explanatory drawing which shows the formation state of the negative electrode side introduction piping in the negative electrode tank of the redox flow battery shown in FIG. 1, (A) is the state which the negative electrode side introduction piping opened to the gaseous phase of the negative electrode tank, (B ) Is a state where the negative electrode side introduction pipe is open to the liquid phase of the negative electrode tank, (C) is a state where a stirring mechanism is present in the liquid phase in addition to the state of (A), and (D) is a state of (B). It is a figure which shows the state which has a stirring mechanism in a liquid phase in addition to.
- 3 is a schematic diagram of a redox flow battery shown in Embodiment 2.
- FIG. 6 is a graph showing the relationship between the number of operating days of the redox flow battery shown in Test Example 1 and the battery capacity (Ah).
- FIG. 1 An outline of a redox flow battery (hereinafter referred to as RF battery) 1 using Mn ions as a positive electrode active material and Ti ions as a negative electrode active material will be described with reference to FIGS.
- a solid line arrow in FIG. 1 means charging, and a broken line arrow means discharging.
- the metal ion shown in FIG. 1 has shown the typical form, and forms other than illustration may be included.
- FIG. 1 shows Ti 4+ as tetravalent Ti ions, but other forms such as TiO 2+ may also be included.
- the RF battery 1 typically includes a power generation unit (for example, a solar power generator, a wind power generator, other general power plants, etc.) and power via an AC / DC converter. It is connected to a load such as a grid or a customer, is charged using the power generation unit as a power supply source, and is discharged using the load as a power supply target. Similar to the conventional RF battery, the RF battery 1 includes a battery element 100 and a circulation mechanism (tank, piping, pump) that circulates the electrolyte in the battery element 100.
- a power generation unit for example, a solar power generator, a wind power generator, other general power plants, etc.
- AC / DC converter AC / DC converter
- the RF battery 1 is different from the conventional one in that Mn ions are used as the positive electrode active material of the positive electrode electrolyte solution, and a configuration for suppressing a decrease in battery capacity due to charge / discharge (a negative electrode side introduction pipe 10 and The negative electrode side supply mechanism 11) is provided.
- a negative electrode side introduction pipe 10 and The negative electrode side supply mechanism 11 a configuration for suppressing a decrease in battery capacity due to charge / discharge.
- the battery element 100 provided in the RF battery 1 includes a positive electrode cell 102 incorporating a positive electrode 104, a negative electrode cell 103 incorporating a negative electrode 105, and a diaphragm 101 that separates the cells 102 and 103 and transmits ions.
- a positive electrode tank 106 that stores a positive electrode electrolyte is connected to the positive electrode cell 102 via pipes 108 and 110.
- a negative electrode tank 107 for storing a negative electrode electrolyte solution is connected to the negative electrode cell 103 via pipes 109 and 111.
- the pipes 108 and 109 are provided with pumps 112 and 113 for circulating the electrolyte solution of each electrode.
- the battery element 100 uses the pipes 108 to 111 and the pumps 112 and 113 to the positive electrode cell 102 (positive electrode 104) and the negative electrode cell 103 (negative electrode 105), respectively.
- the negative electrode electrolyte solution 107 is circulated and charged in accordance with the valence change reaction of metal ions (Mn ions for the positive electrode and Ti ions for the negative electrode) that become the active material in the electrolyte solution of each electrode. Discharge.
- the battery element 100 is normally used in a form called a cell stack in which a plurality of layers are stacked.
- the cells 102 and 103 constituting the battery element 100 discharge a bipolar plate (not shown) in which a positive electrode 104 is disposed on one surface and a negative electrode 105 on the other surface, a liquid supply hole for supplying an electrolytic solution, and an electrolytic solution.
- a configuration using a cell frame having a drain hole to be formed and having a frame (not shown) formed on the outer periphery of the bipolar plate is representative.
- the liquid supply hole and the drainage hole constitute an electrolyte flow path, and the flow path is connected to the pipes 108 to 111.
- the cell stack is configured by repeatedly stacking a cell frame, a positive electrode 104, a diaphragm 101, a negative electrode 105, a cell frame,.
- As the basic configuration of the RF battery a known configuration can be used as appropriate.
- Electrode As the positive and negative electrolytes used in the RF battery 1 of the present embodiment, a common one containing Mn ions and Ti ions is used. On the positive electrode side, Mn ions work as a positive electrode active material, and on the negative electrode side, Ti ions work as a negative electrode active material. Further, Ti ions on the positive electrode side suppress the precipitation of MnO 2 for unknown reasons. Each concentration of Mn ions and Ti ions is preferably 0.3M or more and 5M or less.
- H 2 SO 4, K 2 SO 4, Na 2 SO 4, H 3 PO 4, H 4 P 2 O 7, K 2 PO 4, Na 3 PO 4, K 3 PO 4, HNO 3 at least one aqueous solution selected from KNO 3 and NaNO 3 can be used.
- the negative electrode side introduction pipe 10 is a pipe for introducing an oxidizing gas into the negative electrode tank 107.
- the oxidizing gas pure oxygen, air, ozone and the like can be used.
- the negative electrode side introduction pipe 10 only needs to communicate with the negative electrode tank 107.
- the anode tank 107 is opened in the gas phase
- the anode tank 107 is opened in the liquid phase. Is mentioned.
- it can also be set as the form which added the stirring mechanism 12, such as a screw, to the structure of FIG. 2 (A) or (B).
- the negative electrode tank 107 is provided with an open valve (not shown) so that the pressure in the negative electrode tank 107 does not become unnecessarily high even if the oxidizing gas is introduced from the negative electrode side introduction pipe 10. .
- the negative electrode side introduction pipe 10 is provided with an opening / closing mechanism such as a valve, so that communication / non-communication of the negative electrode side introduction pipe 10 can be controlled. It is preferable that the negative electrode side introduction pipe 10 is closed at all times to suppress evaporation of the negative electrode electrolyte.
- the negative electrode side supply mechanism 11 is configured to introduce an oxidizing gas into the negative electrode tank 107 through the negative electrode side introduction pipe 10.
- a blower when the negative electrode side introduction pipe 10 is in gas phase communication
- a pressure feed pump or the like can be used.
- the RF battery 1 may include a monitor cell for monitoring the battery capacity.
- the monitor cell is basically a single cell smaller than the battery element 100 having the same configuration as that of the battery element 100.
- the monitor cell receives positive and negative electrolytes from the positive electrode tank 106 and the negative electrode tank 107, and Similarly, an electromotive force is generated.
- the battery capacity of the RF battery 1 can be known from the electromotive force.
- trivalent Ti (Ti 3+ ) is brown and tetravalent Ti (Ti 4+ ) is almost colorless and transparent, it is oxidized when the decrease in transparency of the negative electrode electrolyte is confirmed visually or by spectroscopic analysis or light transmittance.
- the introduction of the oxidizing gas is started, and the introduction of the oxidizing gas is preferably terminated with the increase in transparency.
- the introduction of the oxidizing gas may be performed simultaneously with the operation of the RF battery 1.
- the RF battery 1 can be operated while suppressing a decrease in the battery capacity of the RF battery 1.
- the negative electrode side introduction pipe 10 is not opened constantly but is opened intermittently.
- FIG. 3 is a simple drawing showing only the connection state of each pipe.
- the RF battery 2 of the second embodiment includes a gas phase communication pipe 13, a liquid phase communication pipe 14, a positive electrode side introduction pipe 15, and a positive electrode side supply mechanism 16.
- the gas phase communication pipe 13 is a pipe that communicates the gas phase of the positive electrode tank 106 and the gas phase of the negative electrode tank 107.
- oxygen generated by a side reaction on the positive electrode side with charge / discharge can be introduced into the negative electrode tank 107. It is preferable to provide a valve or the like in the gas-phase communication pipe 13 so that communication / non-communication between the tanks 106 and 107 can be adjusted.
- the liquid phase communication pipe 14 is a pipe that communicates the liquid phase of the positive electrode tank 106 and the liquid phase of the negative electrode tank 107. By providing the liquid phase communication pipe 14, the electrolyte solution in both tanks 106 and 107 can be mixed.
- the liquid phase communication pipe 14 is provided with a valve or the like so that the electrolytes stored in the tanks 106 and 107 are not mixed during charging and discharging.
- both electrolytic solutions may be electrolytic solutions containing Mn ions and Ti ions.
- Mn ions function as a positive electrode active material
- Ti ions function as a negative electrode active material.
- the positive electrode side introduction pipe 15 and the positive electrode side supply mechanism 16 can adopt the same configuration as the negative electrode side introduction pipe 10 and the negative electrode side supply mechanism 11, respectively.
- a stirring mechanism is preferably provided in the liquid phase of the positive electrode tank 106 as in the first embodiment.
- the gas phase communication pipe 13 When charging / discharging with the RF battery 2, the gas phase communication pipe 13 is basically opened, and the liquid phase communication pipe 14 is closed. On the other hand, when the battery capacity of the RF battery 2 is recovered, the gas phase communication pipe 13 is opened and the liquid phase communication pipe 14 is also opened. By opening the liquid phase communication tube 14, the positive and negative electrolytes are mixed together, and the RF battery 2 is quickly discharged. Then, an oxidizing gas is introduced from the negative electrode side introduction pipe 10 into the negative electrode tank 107, and an oxidizing gas is also introduced from the positive electrode side introduction pipe 15 into the positive electrode tank 106. At that time, if the tanks 106 and 107 are provided with a stirring mechanism, the stirring mechanism may be operated.
- the timing for recovering the battery capacity of the RF battery 2, the introduction amount of the oxidizing gas, and the timing of the end of the introduction are the same as those in the first embodiment.
- Transparency can be used.
- the solution of Mn 3+ is colored, and the solution of Mn 2+ is almost colorless and transparent.
- the transparency of the electrolyte Becomes higher.
- the Ti 4+ solution that becomes dominant in the electrolyte is almost colorless and transparent. Therefore, the transparency of the mixed electrolyte obtained in a state where the battery capacity is reduced is low, and the transparency of the mixed electrolyte in a state where the battery capacity is restored by the oxidizing gas is increased.
- an RF battery 2 having the same configuration as that of Embodiment 2 described with reference to FIG. 3 was produced.
- As the positive electrode electrolyte and the negative electrode electrolyte an electrolyte mixed with sulfuric acid having a concentration of 2M, 1M MnSO 4 (Mn 2+ ), and 1M TiOSO 4 (Ti 4+ ) was used.
- the positive and negative electrolytes were 3 L each, and sealed in the respective tanks 106 and 107 in an airtight state with external air. Nitrogen gas was sealed in the gas phase portion to suppress oxidation.
- the battery element 100 used was a single cell having an electrode area of 500 cm 2 to which a carbon felt electrode and a cation exchange membrane were applied.
- the liquid phase communication pipe 14 and the gas phase communication pipe 13 were both closed.
- a charge / discharge test was conducted using the Ti / Mn RF battery 2 thus fabricated.
- the initial performance was a current efficiency of 99%, a cell resistivity of 1.5 ⁇ cm 2 , and a battery capacity of 45 Ah.
- the battery capacity of the RF battery 2 was continued.
- the battery capacity of the RF battery 2 reached about 65% of the initial value about 65 days after the start of the operation, the operation of the RF battery 2 was once stopped. Note that both the liquid-phase communication pipe 14 and the gas-phase communication pipe 13 were closed during the operation period of the RF battery 2.
- the liquid phase communication tube 14 was opened, and the positive electrode electrolyte and the negative electrode electrolyte were sufficiently mixed, whereby the RF battery 2 was completely discharged.
- the electrolyte solution mixed at this time was black (colored and opaque).
- the present invention is not limited to the above-described embodiment, and can be appropriately modified and implemented without departing from the gist of the present invention.
- V ions or Cr ions can be used as the negative electrode active material of the negative electrode electrolyte used.
- the structure of Embodiment 1 on the assumption that positive and negative electrolytes are not mixed is employed.
- the redox flow battery of the present invention has a large capacity for the purpose of stabilizing fluctuations in power generation output, storing electricity when surplus of generated power, load leveling, etc., for power generation of new energy such as solar power generation and wind power generation. It can utilize suitably for a storage battery.
- the redox flow battery of the present invention can be suitably used as a large-capacity storage battery that is provided in a general power plant and is intended for measures against instantaneous voltage drop / power outage and load leveling.
- the operating method of the redox flow battery of the present invention can be suitably used when the redox flow battery of the present invention is used in the above various applications.
- 1, 2, redox flow battery 100 battery element, 101 diaphragm, 102 positive electrode cell, 103 negative electrode cell, 104 positive electrode, 105 negative electrode, 106 positive electrode tank, 107 negative electrode tank, 108, 109, 110, 111 piping, 112 , 113 pump, 10 negative electrode side introduction pipe, 11 negative electrode side supply mechanism, 12 stirring mechanism, 13 vapor phase communication pipe, 14 liquid phase communication pipe, 15 positive electrode side introduction pipe, 16 positive electrode side supply mechanism.
Abstract
Description
本発明レドックスフロー電池は、正極電極と、負極電極と、これら両電極間に介在される隔膜とを備える電池要素に、正極用タンクに貯留される正極電解液、及び負極用タンクに貯留される負極電解液を供給して充放電を行うレドックスフロー電池である。この本発明レドックスフロー電池における正極電解液は、正極活物質としてMnイオンを含有し、負極電解液は、負極活物質としてTiイオン、Vイオン、およびCrイオンの少なくとも1種を含有する。そして、本発明レドックスフロー電池は、負極用タンクの外部から内部に連通され、その負極用タンク内部に酸化性気体を導入するための負極側導入配管と、負極側導入配管を介して負極用タンク内部に酸化性気体を供給する負極側供給機構と、を備えることを特徴とする。 Based on the examination and knowledge described above, the present invention is defined below.
The redox flow battery of the present invention is stored in a positive electrode electrolyte stored in a positive electrode tank and in a negative electrode tank in a battery element including a positive electrode, a negative electrode, and a diaphragm interposed between the two electrodes. It is a redox flow battery that charges and discharges by supplying a negative electrode electrolyte. The positive electrode electrolyte in the redox flow battery of the present invention contains Mn ions as the positive electrode active material, and the negative electrode electrolyte contains at least one of Ti ions, V ions, and Cr ions as the negative electrode active material. The redox flow battery of the present invention communicates from the outside to the inside of the negative electrode tank, and the negative electrode side introduction pipe for introducing the oxidizing gas into the negative electrode tank, and the negative electrode tank through the negative electrode side introduction pipe And a negative electrode side supply mechanism for supplying an oxidizing gas therein.
<<全体構成>>
以下、正極活物質としてMnイオン、負極活物質としてTiイオンを用いたレドックスフロー電池(以下、RF電池)1の概要を図1,2に基づいて説明する。図1における実線矢印は、充電、破線矢印は、放電を意味する。なお、図1に示す金属イオンは代表的な形態を示しており、図示される以外の形態も含み得る。例えば、図1では、4価のTiイオンとしてTi4+を示すが、TiO2+などのその他の形態も含み得る。 <Embodiment 1>
<< Overall structure >>
Hereinafter, an outline of a redox flow battery (hereinafter referred to as RF battery) 1 using Mn ions as a positive electrode active material and Ti ions as a negative electrode active material will be described with reference to FIGS. A solid line arrow in FIG. 1 means charging, and a broken line arrow means discharging. In addition, the metal ion shown in FIG. 1 has shown the typical form, and forms other than illustration may be included. For example, FIG. 1 shows Ti 4+ as tetravalent Ti ions, but other forms such as TiO 2+ may also be included.
RF電池1に備わる電池要素100は、正極電極104を内蔵する正極セル102と、負極電極105を内蔵する負極セル103と、両セル102,103を分離すると共にイオンを透過する隔膜101と、を備える。正極セル102には、正極電解液を貯留する正極用タンク106が配管108,110を介して接続される。負極セル103には、負極電解液用を貯留する負極用タンク107が配管109,111を介して接続される。配管108,109には、各極の電解液を循環させるためのポンプ112,113を備える。電池要素100は、配管108~111、ポンプ112,113を利用して、正極セル102(正極電極104)、負極セル103(負極電極105)にそれぞれ正極用タンク106の正極電解液、負極用タンク107の負極電解液を循環供給して、各極の電解液中の活物質となる金属イオン(正極にあってはMnイオン、負極にあってはTiイオン)の価数変化反応に伴って充放電を行う。 [Battery elements and circulation mechanism]
The
本実施形態のRF電池1に用いられる正負の電解液には、MnイオンとTiイオンを含有する共通のものを使用している。正極側にあってはMnイオンが正極活物質として働き、負極側にあってはTiイオンが負極活物質として働く。また、正極側におけるTiイオンは、理由は不明ではあるが、MnO2の析出を抑制する。Mnイオン及びTiイオンの各濃度はいずれも0.3M以上5M以下とすることが好ましい。 [Electrolyte]
As the positive and negative electrolytes used in the RF battery 1 of the present embodiment, a common one containing Mn ions and Ti ions is used. On the positive electrode side, Mn ions work as a positive electrode active material, and on the negative electrode side, Ti ions work as a negative electrode active material. Further, Ti ions on the positive electrode side suppress the precipitation of MnO 2 for unknown reasons. Each concentration of Mn ions and Ti ions is preferably 0.3M or more and 5M or less.
負極側導入配管10は、負極用タンク107の内部に酸化性気体を導入するための配管である。酸化性気体としては、純粋酸素、空気、オゾンなどを利用することができる。この負極側導入配管10は、負極用タンク107に連通していれば良い。例えば、図2(A)に示すように、負極用タンク107の気相に開口している形態、図2(B)に示すように、負極用タンク107の液相に開口する形態とすることが挙げられる。その他、図2(C)や(D)に示すように、図2(A)や(B)の構成にさらにスクリューなどの撹拌機構12を加えた形態とすることもできる。なお、負極用タンク107には、図示しない開放弁が設けられており、負極側導入配管10から酸化性気体を導入しても、いたずらに負極用タンク107の圧力が高くならないようになっている。 [Negative electrode side piping]
The negative electrode
負極側供給機構11は、上記負極側導入配管10を介して負極用タンク107の内部に酸化性気体を導入するための構成である。例えば、送風機(負極側導入配管10が気相連通の場合)や、圧送ポンプなどを利用することができる。 [Negative electrode supply mechanism]
The negative electrode
図示しないが、RF電池1は、電池容量を監視するモニタセルを備えていても良い。モニタセルは基本的に電池要素100と同一の構成を備える電池要素100よりも小型の単セルであり、正極用タンク106と負極用タンク107から正負の電解液の供給を受けて、電池要素100と同様に起電力を生じる。その起電力からRF電池1の電池容量を知ることができる。 [Others]
Although not shown, the RF battery 1 may include a monitor cell for monitoring the battery capacity. The monitor cell is basically a single cell smaller than the
上記構成を備えるRF電池1を運転する(充放電を繰り返す)と、徐々に電池容量が低下していく。その場合、RF電池1を完全放電状態とすると共に、上述した負極側導入配管10を開放し、負極側供給機構11を動作させて、負極用タンク107の内部に酸化性気体を導入する。酸化性気体を導入するタイミングの判断、酸化性気体の導入量の判断は、RF電池1にモニタセルが備わっている場合はモニタセルで検知される起電力に基づいて行えば良い。その他、負極電解液の透明度により上記判断を行うこともできる。3価のTi(Ti3+)は褐色、4価のTi(Ti4+)はほぼ無色透明であるので、負極電解液の透明度の低下を目視あるいは分光分析や光の透過率で確認したら酸化性気体の導入を開始し、同様に透明度の上昇をもって酸化性気体の導入を終了すると良い。 << Operation method of RF battery >>
When the RF battery 1 having the above configuration is operated (charging / discharging is repeated), the battery capacity gradually decreases. In that case, the RF battery 1 is completely discharged, the negative electrode
実施形態2では、図3に基づいて、実施形態1の構成にさらに付加的な構成を備えるRF電池2を説明する。なお、図3は、各配管の接続状態のみを示す簡易的な図面である。 <
In the second embodiment, an
実施形態2のRF電池2は、実施形態1のRF電池の構成に加えて、気相連通管13と、液相連通管14と、正極側導入配管15と、正極側供給機構16と、を備える。 << Overall structure >>
In addition to the configuration of the RF battery of the first embodiment, the
気相連通管13は、正極用タンク106の気相と、負極用タンク107の気相と、を連通する配管である。気相連通管13を設けることで、充放電に伴って正極側で副反応により発生する酸素を、負極用タンク107に導入することができる。この気相連通管13にはバルブなどを設けて、両タンク106,107間の連通・非連通を調節できるようにしておくことが好ましい。 [Gas-phase communication pipe]
The gas
液相連通管14は、正極用タンク106の液相と、負極用タンク107の液相と、を連通する配管である。液相連通管14を設けることで、両タンク106,107内の電解液を混合させることができる。この液相連通管14には、充放電時に両タンク106,107に貯留される両電解液同士が混合しないように、バルブなどを設けておく。 [Liquid phase communication pipe]
The liquid
正極側導入配管15及び正極側供給機構16はそれぞれ、負極側導入配管10及び負極側供給機構11と同じ構成を採用することができる。 [Positive electrode inlet piping and positive electrode supply mechanism]
The positive electrode
正極用タンク106の液相内には、実施形態1と同様に撹拌機構を設けることが好ましい。 [Others]
A stirring mechanism is preferably provided in the liquid phase of the
上記RF電池2で充放電を行う際は、気相連通管13は基本的に開放しておき、液相連通管14は閉じておく。一方、RF電池2の電池容量を回復させる際は、気相連通管13は開放しておき、液相連通管14も開放する。液相連通管14を開放することで、正負の電解液が混ざり合い、RF電池2は速やかに放電状態となる。そして、負極側導入配管10から負極用タンク107内に酸化性気体を導入すると共に、正極側導入配管15から正極用タンク106内にも酸化性気体を導入する。その際、両タンク106,107内に撹拌機構を備えるのであれば、その撹拌機構を動作させておくと良い。 << Operation method of RF battery >>
When charging / discharging with the
次に、図3を参照して説明した実施形態2と同様の構成を備えるRF電池2を作製した。正極電解液と負極電解液には、濃度2Mの硫酸、1MのMnSO4(Mn2+)、1MのTiOSO4(Ti4+)を混合させた電解液を用いた。正負の電解液は、各々3Lとし、各々のタンク106,107に外部空気と気密した状態で封入した。気相部には酸化を抑制するために窒素ガスを封入した。また、電池要素100には、カーボンフェルト電極、陽イオン交換膜を適用した電極面積500cm2を有する単セルを用いた。また、液相連通管14と気相連通管13は共に閉じておいた。 <Test Example 1>
Next, an
試験例1と同様の構成を備えるRF電池2を用いて、今度は、気相連通管13を開放した状態(液相連通管14は閉)で充放電試験を開始した。そうすることで、試験開始後、電池容量が初期の約65%に低下するまで約90日となり、RF電池2の電池容量の減少速度が緩やかになることを確認した。この結果は、RF電池2の電池容量の減少を効果的に抑制できるといえるほどではなかった。 <Test Example 2>
Using the
Claims (15)
- 正極電極(104)と、負極電極(105)と、これら両電極間に介在される隔膜(101)とを備える電池要素(100)に、正極用タンク(106)に貯留される正極電解液、及び負極用タンク(107)に貯留される負極電解液を供給して充放電を行うレドックスフロー電池(1)であって、
前記正極電解液は、正極活物質としてMnイオンを含有し、
前記負極電解液は、負極活物質としてTiイオン、Vイオン、およびCrイオンの少なくとも1種を含有し、
前記負極用タンク(107)の外部から内部に連通され、その負極用タンク(107)内部に酸化性気体を導入するための負極側導入配管(10)と、
前記負極側導入配管(10)を介して前記負極用タンク(107)内部に前記酸化性気体を供給する負極側供給機構(11)と、
を備えることを特徴とするレドックスフロー電池(1)。 A positive electrode electrolyte stored in a positive electrode tank (106) in a battery element (100) comprising a positive electrode (104), a negative electrode (105), and a diaphragm (101) interposed between the two electrodes; And a redox flow battery (1) for supplying and discharging a negative electrode electrolyte stored in a negative electrode tank (107),
The positive electrode electrolyte contains Mn ions as a positive electrode active material,
The negative electrode electrolyte contains at least one of Ti ions, V ions, and Cr ions as a negative electrode active material,
A negative electrode side introduction pipe (10) communicating from the outside to the inside of the negative electrode tank (107) and for introducing an oxidizing gas into the negative electrode tank (107);
A negative electrode side supply mechanism (11) for supplying the oxidizing gas into the negative electrode tank (107) through the negative electrode side introduction pipe (10);
A redox flow battery (1) comprising: - 前記酸化性気体は、酸素を含有する気体であることを特徴とする請求項1に記載のレドックスフロー電池(1)。 The redox flow battery (1) according to claim 1, wherein the oxidizing gas is a gas containing oxygen.
- 前記正極用タンク(106)の気相と、前記負極用タンク(107)の気相と、を連通する気相連通管(13)を備えることを特徴とする請求項1に記載のレドックスフロー電池(1)。 The redox flow battery according to claim 1, further comprising a gas phase communication pipe (13) for communicating the gas phase of the positive electrode tank (106) and the gas phase of the negative electrode tank (107). (1).
- 前記レドックスフロー電池(1)の充電状態をモニタするモニタ機構を備えることを特徴とする請求項1に記載のレドックスフロー電池(1)。 The redox flow battery (1) according to claim 1, further comprising a monitor mechanism for monitoring a charge state of the redox flow battery (1).
- 前記負極側導入配管(10)は、前記負極用タンク(107)の液相内に開口していることを特徴とする請求項1に記載のレドックスフロー電池(1)。 The redox flow battery (1) according to claim 1, wherein the negative electrode side introduction pipe (10) is opened in a liquid phase of the negative electrode tank (107).
- 前記負極用タンク(107)内部に設けられ、前記負極電解液を撹拌する撹拌機構(12)を備えることを特徴とする請求項1に記載のレドックスフロー電池(1)。 The redox flow battery (1) according to claim 1, further comprising a stirring mechanism (12) provided in the negative electrode tank (107) and stirring the negative electrode electrolyte.
- 前記正極電解液は、Tiイオンを含有することを特徴とする請求項1に記載のレドックスフロー電池(1)。 The redox flow battery (1) according to claim 1, wherein the positive electrode electrolyte contains Ti ions.
- 前記負極電解液は、負極活物質としてTiイオンを含有し、さらにMnイオンを含有することを特徴とする請求項7に記載のレドックスフロー電池(1)。 The redox flow battery (1) according to claim 7, wherein the negative electrode electrolyte contains Ti ions as a negative electrode active material and further contains Mn ions.
- 前記正極用タンク(106)の液相と、負極用タンク(107)の液相と、を連通する液相連通管(14)を備えることを特徴とする請求項8に記載のレドックスフロー電池(1)。 The redox flow battery according to claim 8, further comprising a liquid phase communication pipe (14) that communicates the liquid phase of the positive electrode tank (106) and the liquid phase of the negative electrode tank (107). 1).
- 前記正極用タンク(106)の外部から内部に連通され、その正極用タンク(106)内部に酸化性気体を導入するための正極側導入配管(15)と、
前記正極側導入配管(15)を介して前記正極用タンク(106)内部に前記酸化性気体を供給する正極側供給機構(16)と、
を備えることを特徴とする請求項9に記載のレドックスフロー電池(1)。 A positive electrode side introduction pipe (15) that communicates from the outside to the inside of the positive electrode tank (106) and introduces an oxidizing gas into the positive electrode tank (106);
A positive electrode side supply mechanism (16) for supplying the oxidizing gas into the positive electrode tank (106) through the positive electrode side introduction pipe (15);
The redox flow battery (1) according to claim 9, characterized by comprising: - 請求項1に記載のレドックスフロー電池(1)を用いたレドックスフロー電池(1)の運転方法であって、
前記負極電解液に含まれる負極活物質を酸化するために、前記負極用タンク(107)内部に前記酸化性気体を導入することを特徴とするレドックスフロー電池(1)の運転方法。 A method for operating a redox flow battery (1) using the redox flow battery (1) according to claim 1,
A method for operating a redox flow battery (1), wherein the oxidizing gas is introduced into the anode tank (107) in order to oxidize an anode active material contained in the anode electrolyte. - 前記酸化性気体の導入は、前記正極電解液と前記負極電解液の充電状態が異なったときに行うことを特徴とする請求項11に記載のレドックスフロー電池(1)の運転方法。 The operating method of the redox flow battery (1) according to claim 11, wherein the introduction of the oxidizing gas is performed when the positive electrode electrolyte and the negative electrode electrolyte are charged differently.
- 前記酸化性気体の導入量を制御することで、前記正極電解液と前記負極電解液の充電状態をほぼ同じ状態にすることを特徴とする請求項12に記載のレドックスフロー電池(1)の運転方法。 The operation of the redox flow battery (1) according to claim 12, wherein the charged state of the positive electrode electrolyte and the negative electrode electrolyte is made substantially the same by controlling the amount of the oxidizing gas introduced. Method.
- 前記導入量を制御する基準として、前記負極電解液の透明度を用いることを特徴とする請求項13に記載のレドックスフロー電池(1)の運転方法。 The operation method of the redox flow battery (1) according to claim 13, wherein the transparency of the negative electrode electrolyte is used as a reference for controlling the introduction amount.
- 前記レドックスフロー電池(1)の充電状態をモニタリングしながら運転することを特徴とする請求項11に記載のレドックスフロー電池(1)の運転方法。 The operation method of the redox flow battery (1) according to claim 11, wherein the operation is performed while monitoring a charging state of the redox flow battery (1).
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JP5007849B1 (en) | 2012-08-22 |
TW201246681A (en) | 2012-11-16 |
EP2541660A1 (en) | 2013-01-02 |
KR101265863B1 (en) | 2013-05-20 |
CN102859775B (en) | 2014-08-06 |
US8632903B2 (en) | 2014-01-21 |
EP2541660B1 (en) | 2014-10-08 |
US20130157162A1 (en) | 2013-06-20 |
KR20130020884A (en) | 2013-03-04 |
CA2789889A1 (en) | 2012-09-25 |
CN102859775A (en) | 2013-01-02 |
ZA201207543B (en) | 2013-05-29 |
TWI412173B (en) | 2013-10-11 |
AU2011362015B2 (en) | 2013-06-27 |
JP2012204135A (en) | 2012-10-22 |
ES2517466T3 (en) | 2014-11-03 |
CA2789889C (en) | 2013-08-20 |
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EP2541660A4 (en) | 2013-09-25 |
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